Tertiaryaminocyclobutanones and their production



United States Patent New Jersey No Drawing. Filed May 26, 19 61, Ser.No. 112,789 20 Claims. (Cl. 260-247.7)

This application is a continuation-impart of my copending U.S.application Serial No. 71,397, Substituted Cyclobutanones, filedNovember 25, 1960, now abandoned.

This invention relates to cyclobutane derivatives.

It is an object of this invention to provide novel substitutedcyclobutanones.

It is another object of this invention to provide novel cyclobutanederivatives by a novel process.

It is another object of this invention to provide a new class ofcyclobutane derivatives that are useful chemical intermediates.

Other objects of the invention will be apparent from the description andclaims which follow.

The novel compounds of the invention are substituted cyclobutanecompounds containing a ketone radical and a tertiary amine radical andhave the structural formula:

wherein R and R are hydrogen or monovalent organic radicals or divalentorganic radicals which, together with the adjacent carbon atom on thecyclobntane ring, form an organic ring, wherein R and R can be the sameradicals as R and R and wherein X is a tertiary amine radical having anitrogen atom attached to the adjacent carbon atom on the cyclobutanering. The substituent X typically 'has the formula In the above formulasR and R are typically: (a) alkyl radicals having 1 .to 18 carbon atoms;(b) phenyl radicals; (c) thienyl radicals; (d) allyl radicals; (e)carbon and hydrogen atoms which, together with the adjacent carbon atomon the cyclobutane ring, form a carbocyclic ring containing 5 to 7carbon atoms such as cyclopentane, cyclohexane, norbornane, norborneneand related rings; (f) carbalkoxy radicals wherein the alkoxy 'pyranrings and the like; or (h) hydrogen. As pointed out above, R and R canbe the same radicals as R and R In the above formulas R and R aretypically: (a) alkyl radicals having 1 to 8 carbon atoms; (b) carbon andhydrogen atoms which, together with the nitrogen atom, form aheterocyclic ring containing 4 to 8 carbon atoms such as piperidine,methyl-substituted piperidines, pyrrolidine, 3-azabicyclo[3.2.2]nonaneand related rings; or (c) carbon, hydrogen and oxygen atoms which,together with the nitrogen atom, form a morpholine ring. In the aboveformulas Y and Z are alkylene radicals having 2 to 4 carbon atoms andform such ring structures as piperazine and methyl-substitutedpiperazine rings.

' The above described cyclobutane derivatives can be prepared byreacting ketenes and enamines. The reaction of the invention can berepresented by the following equation wherein the substituents in theformulas are those as described hereinabove:

HRa

The ketene reactant can be ketene (H C=C=O), a monosubstituted oraldoketene (RCH=C=O), or a disubstituted or ketoketene (R C=C=O). Suchcom pounds can be prepared by methods known in the art, for instance, bymethods described in Organic Reactions, John Wiley and Sons, Inc., N.Y.(1946) vol. III,

chap. 3. The disubstituted ketene reactants can also be prepared by themethod described in copending application, H-asek and Elam, U.S. SerialNo. 841,961, filed September 24, 1959. Typical ketenes that can be usedin the process of the invention include: ketene, methylketene,ethylketene, n-propylketene, isopropylketene, n 'butylketene,isobutyllretene, phenylketene, dimethylketene, ethylmet-hylketene,diethylketene, n-rbutylethylketene, dim-propylketene, diisobutylketene,di-nabutylketene, di-n-heptylketene, ethyldodecylketene,distearylketene, camphoketene, di'benzylketene, ditolylketene,diallylketene, dicarbethoxyketene, tetramethyleneketene,pentamethyleneketene, diphenylketene, methylpheny-lketene,allylmethylketene, methylcarbethoxyketene, ethylcarbethoxyketene,npr-opylcarbomethoxyketene, and the like.

One type of enamine reactant that can be used in the process of theinvention is the type of enamine having no S-hydrogen atoms which can beprepared by reacting an aldehyde having one lac-hydrogen atom with asecondary amine. This reaction is described in copending application,Brannock U.S. Serial No. 34,881, filed June 9, 1960. Typical enamines ofthis type that can be used in the process of the invention include:N,N-dimethylisobutenylamine, N,N diethylisobutenylamine, N,Ndibutylisobutenylamine, N -isobutenylpiperidine,N-isobutenylpyr-rolidine, N,N-dimethyl 2 methylbutenylamine,N-(2-methylbutenyl)piperidine, N,N-dimethyl-Z-ethylbutefnylam'ine,N-'(2-ethylbutenyl)piperidirre, N-:(methylenecyclohexyl) dimethylamine,N-(methylenecyclohexyl) piperidine, N-isobutenylmorpholine,N-(Z-ethylhexenyl) morpholine, N-(Z-ethylhexenyl)piperidine,N,N-dimethyl-2-ethylhexenylamine, 3-isobutenyl-3-azabicyclo[3.2.2]nonane, -dimethylaminomethylene-2-norbornene,2-diisopropylaminomethylene-2-(2,3-dihydro-4H-pyran), 2- (2dimethylamino-l-ethyl-vinyl)thiophene,2-dimethylamino-1,1-diphenylethylene, and the like.

Another type of enamine that can be used in the process of the inventionis the type having at least one hydrogen atom'on the fl-carbon atom.Enarnines of this type can be prepared by reacting a secondary aminewithan aldehyde having at least two a-hydrogen atoms. Examples of suchsecondary amines include: simple dialkylamines such as dimethylamine,diethylamine, dibutylamine; heterocyclic secondary amines such aspyrrolidine, piperidine, morpholine, piperazine and l-methylpiperazine;

and secondary aromatic amines such as N-rnethylaniline.i

Typical aldehydes having at least two a-hydrogen atoms include:propionaldehyde, butyraldehyde, valeraldehyde, heptaldehyde,acetaldehyde, phenylacetaldehyde, etc. Examples of a few of theresulting enamines having at least one ,B-hydrogen atom obtained by thereaction of such secondary amines and aldehydes include:N-(l-butenyl)piperidine, N,N-dimethylvinylamine, N,N-dimeth-.ylpropenylamine, N-(1-butenyl)pynrol-idine,N,N-dimethyl-l-butenylamine, N,N-dibutyl-l butenylamine,N-(lheptenyl)morpholine, and the like.

Although the reactions employing any' of the types of ketenes andenamines discussed above and the novel compounds having thecyclobutanone structure obtained by such reactions are within the scopeof the invention, it should be noted that there are significantdifierences between certain classes of the reactants and products. Thus,when the process of the invention employs a ketoketene,

such as a dialkylketene, and an enamine having no ,8- hydrogen atoms,i.e., an enamine prepared from aldehydeshaving one a-hydrogen'atom, theresulting product is a substituted cyclobutanone having no hydrogenatoms on the carbon atoms adjacent to the carbonyl group. In

other Words, R R R and R are substituents other than hydrogen atoms.Compounds of this type are characterized by superior thermal stability,

When the reaction is carried out with a ketene having at least onea-hydrogen atom or an enamine having at least oneQB-hydrogen atom, theresulting substituted cyclogen atom on a carbon adjacent to the carbonylgroup. In other Words, at least one of the substituents, R R R 'or R isa hydrogen atom. Compounds of this type are useful new compounds but arenot so stable thermally as the other cyclic compounds of the invention.In order to obtain such compounds in good yield, the reaction of theketene and the enamine must be'carried out at a temperature below about0., preferably below about 10 C., and to avoid decomposition of thecompounds they must not be heated to temperatures above about 50 C. forany substantial length of time. As a general rule it can be said thatthe thermal stability of the cyclic compounds of the invention increaseswith an increase in the size of the alkyl substituents on the carbonatoms adjacent to the carbonyl group. For example, a compound of theinvention in which the substituents R R R and R are methyl groups isless stablethermally than a compound otherwise identical'in structurebut in which R R R and R are butyl groups. This principle will influencethe choice'of a particular temperaturebelow' about 50 C. for preparingany specific compound in the class of invention; i

The molar proportion of the enamine reactant to the ketene can be widelyvaried as the resulting cyclobutane product can be readily separatedfrom excess or unrethe less stable compounds of the butanone product ofthe invention has at least one hydro- 7 acted reactants. Substantiallystoichiometric amounts of the reactants are more'generally utilized inaccordance However, such enamines as 1,4-diisobutenylpiperazine reactwith two molar proportions of such ketenes as dimethylketene in thepresent process as represented by the following equation:

The subject reaction to prepare the cyclobutane derivatives of theinvention proceeds readily in the absence of catalyst materials. Thereaction can be conveniently etfected by merely combining the reactantsat room temperature. Reaction temperature in the 'rangeof about 0 -80 C.to 200 C. can be utilized, although reaction temperatures of about 0 C.to100' C. are preferred. As I have already indicated, if the ketene hasan a-hydrogen atom or if the enaminehas'a fi-hydrogen atom, the reactiontemperature must be maintained below about 50 C. in order to obtain thesubstituted cyclobutanone product of the invention. The optimum reactiontemperature varies with such factors as the thermal stability of thedesired product and the reactivities of the enamine and the ketene,'thehigher temperatures being preferred for the higher molecular weightreactants.

The present reaction time can be widely varied. Typical reaction timesvary from a few minutes to 24 hours to several days, the reaction timevarying with such variables as the reaction temperature and thereactivityof the reactants.

The present reaction is conveniently effected under atmosphericpressure, although higher pressures'or even subatmospheric'pressures'can be utilized.

The reaction of the invention can be run with or without a solvent.However, if a solvent is used, solvents that function as solvents forthe rcactantsand the reaction products and which are substantially inertin the reaction are utilized in accordance with usual practice) Typicalreaction solventsj include aliphatic esters such as ethyl acetate,ethers such as diethyl ether and diisoprop yl ether,

chlorinated aliphatic hydrocarbons such as chloroform and carbontetrachloride, and aliphatic and aromatic hy-' drocarbons such asn-hexane, n-octane, benzene and V toluene.

The present reaction of the described enamines and ketenes proceeds inhigh yields to form the described cyclobutane derivatives. Thecyclobutane derivative product can be worked-up or purified byconventional purification methods, the preferred method varying with theproperties of the product. Particularly efiective purification methodsinclude fractional distillation under re-' duced pressure and fractionalcrystallization from solvents. However, other purification methods suchas solvent extraction, chromatographic adsorption and the like can alsobe utilized.

The cyclobutane derivatives of the invention have both tertiary amineand ketone groups. The ketone group on such derivatives can be readilyreduced to an alcohol group with an alkaline metal hydride such assodium borohydride or the like. The resulting amino alcohol can then beconverted to the corresponding methacrylate ester by reactingmethacrylyl chloride therewith which, when copolymerized withacrylonitrile, results in a fiberforming polymer that has betterdyeability than unmodified polyacrylonitrile. The cyclobutanederivatives of the invention also are useful intermediates in thepreparation of pharmaceuticals such as analgesics. The utility of thecompounds of the invention is further disclosed in Brannock and Martinapplication titled Tertiary Amino Alcohols of the Cyclobutane Series,Serial No. 71,398, filed November 25, 1960, now abandoned, and in thecontinuation-in-part application Serial No. 112,794 of the sameapplicants and title filed concurrently herewith.

It should be noted also that the amino alcohols prepared from the ketonecompounds of the present invention have good thermal stability, evenwhen prepared from the compounds having hydrogen atoms attached to acarbon atom adjacent to the carbonyl group. Accordingly, hydrogenationof the ketone to the corresponding alcohol provides a means forpreserving the ring structure of the less stable compounds of theinvention.

The invention is illustrated by the following examples of preferredembodiments thereof.

EXAMPLE 1 Into a 3-neck flask equipped with a stirrer and a Dry Icecondenser was charged 2400 g. (24 moles) of N,N-dimethylisobutenylamine.After the system was flushed with nitrogen, about 12 moles ofdimethylketene was passed in over a period of 7 hrs. The reaction vesselwas cooled in an ice bath. After standing for 24 hrs. at roomtemperature, the reaction solution was examined by gas chromatographyand found to consist primarily of unreacted N,N-dimethylisobutenylamine,dimethylketene dimer and the product,3-dimethylamino-2,2,4,4-tetramethylcyclobutanone, together with 2 minorcomponents. Distillation through a 4-ft. Podbielniak Helipak column gave1850 g. of recovered N,N-dimethylisobutenylamine and 842.7 g., B.P.9192.5 C. (27.5 mm.), (purity 95% by gas chromatography) of3-dimethylamino-2,2,4,4-tetramethylcyclobutanone. This is a yield of 86%based on N,N-dimethylisobutenylamine consumed. In order to obtain asample for analysis some of the 95 material was dissolved in dilutehydrochloric acid, extracted with ether, neutralized with sodiumhydroxide and extracted with ether. The organic layer was washed withWater, then dried over anyhdrous magnesium sulfate and distilled throughan 8-in. Vigreux column, B.P. 92 C. (27 min), 1: 1.4439.

Analysis.-Calcd. for C H NO: C, 71.1; H, 11.2; N, 8.3; neut. equiv, 169.Found: C, 71.3; H, 11.2; N, 8.1; neut. equiv., 170.

EXAMPLE 2 To a solution of 210 g. (1.5 moles) of N-isobutenylpiperidinein 1000 ml. of ethyl ether at room temperature was added approximately70 g. (1 mole) of dimethylketene. The reaction flask was stoppered andallowed to stand for two days at room temperature. Distillation of thereaction solution gave 125.2 g. of recovered N-isobutenylpiperidine and94.3 g. (76% based on N-isobutenylpiperidine consumed) of2,2,4,4,-tetramethyl-3piperidinocyclobutanone, B.P. 97 C. (4.2 mm.).

Analysis-(laid. for C H NO: C, 74.5; H, 11.0; N, 6.7. Found: C, 74.3; H,11.2; N, 6.5.

EXAMPLE 3 To a solution of 99.0 g (1.0 mole) of N,N-dimethy1-isobutenylamine in 300 ml. of hexane was added at room temperature about40 g. (0.48 mole) of ethylmethyl ketene. The reaction solution wasstirred for 4 hr., then allowed to stand for 16 hr. at room temperature,and finally refluxed for 3 hr. Distillation of the resulting solutiongave 61.3 g. of recovered N,N-dimethylisobutenylamine and 58.5 g. (84%based on N,N,-dimethylisobutenylamine consumed) of 3-dimethylamino4-ethyl-2,2,4-trimethylcyclobutanone, B.P. 96 C. (25 mm.). This samplewas about 96% pure by gas chromatography. After treatment by the methoddescribed in Example 1, the material was pure as determined by gaschromatography.

EXAMPLE 4 To 120 g. (0.67 mole) of 1-piperidylmethylenecyclohexane,which was stirred in a nitrogen atmosphere under a Dry Ice condenser,was added 0.67 mole dirnethyL ketene. A rapid, exothermic reactionoccurred, and the reaction was carried out for about 1 hour. There wasisolated in good yield 2,2-dirnet-hyl-3-piperidino-spiro-[3.51nonan-l-one, M.P. 78-81 C. Recrystallization of an analyticalsample from ethanol gave a material melting at 81-825 C.

Analysis.-Calcd, for C H NO: C, 77.1; H, 10.8; N, 5.6; neu-t. equiv.,249. Found: C, 77.1; H, 11.0; N, 5.4. neut, equiv., 250.

EXAMPLE 6 Following the manner of Example 4, N-isobutenylmorpholine anddimethylketene gave 2,2,4,4-tetramethyl- 3-morpholinocyclobutanone, M.P.5859.5 C.

AnalysiS.-Calcd. for C H NO C, 68.2; H, 10.0; N, 6.6. Found: C, 68.1; H,9.9; N, 6.5.

EXAMPLE 6 Following the manner of Example 4, N-(2-ethyl-1-bHtenyDpiperidine and d-irnethylketene gave 2,2-diethyl-4,4-dimethyl-3-piperidinocyclobutanone, B.P. -112 C. (5 mm.).

Analysis.C-alcd. for C H NO: C, 76.0; H, 11.4; N, 5.9. Found: C, 75.8;H, 11.4; N, 5.8.

EXAMPLE 7 Following the manner of Example 4, N-isobutenyl-2,'6-dimethylpiperidine and dimethylketene gave 2,2,4,4- tetramethyl 3(2,6 dimethylpiperidino)cyclobutanone, B.P. 97-100 C. (2.6 mm.).

Analysis.Calcd. for C H NO: C, 76.0; H, 11.4; N, 5.9. Found: C. 75.7; H,11.1; N, 6.1.

EXAMPLE 8 Using the general method described in Example 2, the

following enam'ines and ketenes produced the tertiaryaminocyclobutanonesset out in the table below.

8' V dimethyl-Z-ethyl-l-butenylamine in 200 m1. of benzene was added 23g. (0.55 mole) of ketene at C. The

Table Ketene Enamine Product B.P C.

(M.P C.)*

Dimethylketene 3-is0butenyl-3-azabieyclo[3.2.2]nonane2,2,4,ftfitiiamethyl-3-(3-azabicyc10[3.2.2]nonau-3-yl) 112-115 eye 0 uanone; l-isobutenyl-i-methylpiperazine2,2,4,4-tetramethyl-3-(4-methy1piperazino)cyclo- 105-107 butanone. (3.mm.) 1,4-diisobuteny1piperazine3,3-(1,4-piperezinediyl)bis[2,2,4,4-tetramethylcyclo- *256 bntanone]. 7(dec.) 5-dimethy1amjnomethylene-2-norbomens4-dimethylamino-3,3-dimethylspiro[cyclobutane-l, 125-127 I2-(5-norbornen)]-2-one. mm) Z-dimethylaminomethyiene-2-(2,3-dihydro-4H4-dimethylamino-3,3-dimethylspiro[cyclobutane-l, 100-103 pyran).2-(2,3-dihydro-4H pyran)]-2-one. mm. N,N-dibutylisobuteny1arnine3-dibutylamino-2,2,4,4-tetramethylcycl0butanone (125-1237 1 mm.1-isobutenyl-1-ethyl-2,5-dimethylpiperazine2,2,4,4-tetramethyl-3-(4-ethyl-2,5-dimethylpiper- 140-143azino)cyclobutanone. (2.5 mm.) 2-(2-dimethylamino-1-ethylvinyl)thiophene3-dimethylamino-2-ethyl-4,4-dimethy1-2-(2-thieny1) 108 cyclobutanone.mm.) 2-dimethy1amino-1,l-diphenylethylene34113111?thylamino-2,2-dimethy1-4,4-diphenylcyclo- 120-121 u anone.N-isobutenylmorpholine Z-ethyl-2,4,4-ttimethyl-3-morpholinocyclobutanone(1 101-10? .3 mm. N ,N-dimethylisobutenylamineB-dimethylamino-Z,2-diethyl-4,4-dimethylcyclo- 95-98 V butanone. (8 mm.)N,N-dimethyl-2-ethyl-l-bntenylalnine3-dimethy1amino-2,2,4,4-tetraethylcyclobntanone- (107-110 5. mm.N-(2-ethyl-1-butenyl)-piperidine3-piperidino-2,2,4,4-tetraethylcyclobutanone (1 130-132 .5 mm.) Do-N-isobutenylmorpholine- 3-mbrph0lin0-2,2-diethyl4,4-dimethylcyc10-118-120 butanone. (5 mm.) Methylpropyl ketene.--N,N-dimethylisobutenylamine3-%int1cthylamin0-2,2,4-trimethyl-4-propylcyclo- (8 94-933 11 anone. mm.Do. N,N-dimethy1-2-ethyl-1-butenylamine3-dimethylamino-Z,2-diethyl-4-methyl-4-propyl- 105 cyclobutanone. (5mm.) Butylethylketene N,N-dimethylisobutenylamine 3%in1ethy1amino-2-buty1-2-ethyl-4;4-dimethylcyclo- (2103-105 u.anone. mm.Diheptylketene .do- 3-dimethylarnino-2,2-diheptyl-4,4-dimethylcyclo-158-159 butanone. (2 mm.) Ethyldodecylketene .do. 3-dimethy1amin0-2-d0decyl-2-ethy1-4,4-dimethy1- 153-156 cyclobutanone. (1 5mm.)Pentamethyleneketene. N-isobutenylpiperidine2,2-din'iethyl-3-pipend1n0spir0[3,5]nonanone *81-82 DiphenylketeneN,N-dimethylisobutenylamine3-%int1ethylamino-Z,2-dm1ethyl-4,4-d1phenylcyclo-' *120-122 V n anone. lDo. N,N-dimcthyl-2-ethyl-l-butenylamine3-dingtethy1amin0-2,2-diethyl-4,4-diphenylcycl0- 102-103 \u anone.Methy1phenylketene. N,N-dimethylisobutenylamine3-dimethylamin0-2,2,4-trimethy1-4-phenylcycl0- 110 butanone. (2 mm.)Allylmethylketene do 2-allyl-3-dimethylam1n02,4,4-tr1methylcyclo- 93-98r butanone. (7 mm.) Ethylcarbethoxyketene do2-carbethoxy-3-dimethy1ammo-2ethyl-4,4-dnnethyl- 140-143 Vcyclobutanone. (0.5 mm.) DimethylketeneN,N-dimethyl-2-methyl-l-octenylamineS-dimethylamin0-2-11exyl-2,4,4-tnmethy1cyc10- 120-122 butanone. (2 mm.)

EXAMPLE 9 lithium aluminum hydride to 2-ethyl-3-piperidinocyclobutanol.

EXAMPLE l0 To a stirred solution of 69.5 g. (0.5 mole.) of N-ibutenylpiperidine in 200 m1. of ether was added 35 g.

(0.5 mole) of dimethylketene. The reaction temperature,

was kept at to 0 C. during the addition, and for 1 hour after theaddition was complete. An infrared spectrum showed that the reactionmixture was a solution of2-ethyl-4,4-dimethyl-3-piperidinocyclobutanone.

- EXAMPLE 11 7 To a stirred solution of 49.5 (0.5 mole) of N,N-dimethyl-isobutenylamine in 200 ml. of ether was added 235g. (0.56 mole)of ketene at to 15. C. The temperature was kept at 20 C. for anadditional hour.

An infrared spectrum showed that the reaction mixture was a solution of2,2-dimethyl-3-dimethylaminocyclobutanone. V V

7 EXAMPLE 12 TO a stirred solution of g. 0.47. mole) of'N,N-

temperature was keptat 0C. for an additional 2 111'. An infraredspectrum showed that the reaction mixturewas a solution of2,2-diethyl-3-dimethylaminocyclobutanone.

EXAMPLE 13 Using the method described in Example 9, the followingenamines and ketenes gave the products indicated:

Ketene Enamine Product Ketene N-isobutenyliminodi- 3,3-(2,2-dimethyi-3-propionitrile. oxocyclobutylimino) djpropionitrile. DoN-isobutenyldibenzyl- 3-dibenzylamino-2,2-diamine. 'methylcyclobutanone.Do N,N-dimethylvinyl- 3-dimethylamiuocyc1oamine. butanone. DoN,N-dimethy1propenyl- 3-din1ethy1amino-2- amine. methylcyclobntanone.Dimethylketene N,N-dimet;hylvinyl- 3-dimethy1amino-2,2-diamine.methylcyclobutanone. Diphenylketene N-(l-butenyDplperidine-3-piperidino-4-ethy1-2,2-

diphenylcyclobuta- H0118.

V EXAMPLE 14 7 To a stirred solution of 50 g. (0.3 mole)ofj-dimethylamino-2,2,4,4-tetramethylcyclobutanone in 75 ml. of ethanolwas added slowly a solution of 3.8 g. (0.1 mole) of sodium iborohydridein 25 ml. of water. The reaction was exothermic, but the temperature waskept at 25- 30 C. by means of a water bath; The reaction mixture wasstirred for 1 hr. after the addition was complete, then heated in anevaporating dish on the steam bath for 1 hr.. To this residue was added300 m1. of

EXAMPLE To a stirred refluxing solution of 34.2 g. (0.2 mole) of3-dimethylamino-2,2,4,4-tetran1ethylcyclobutanol in 200 ml. of benzenewas added dr-opwise a solution of 20.9 g. (0.2 mole) of methacrylylchlonide in 50 ml. of benzene. The addition required 30 min. andrefluxing was continued for an additional 30 min. After cooling, 100 ml.of water was added. The solution was then neutralized with sodiumbicarbonate solution. The organic layer was separated, washed with waterand dried over anhydrous magnesium sulfate. Distillation of thissolution through a 6-in. Vigreux column gave 38.3 g. (80%) of3-dimethylamino 2,2,4,4 tetramethylcyclobutanol methacrylate, B.P. 71-74C. 1 mm.).

EXAMPLE 16 A mixture consisting of 38 g. of acrylonitrile, 2 g. of3-dimethylamino-2,2,4,4-tetramethylcyclobutanol methacrylate, 0.14 g. ofthe hydrochloride of 2,2'-dig1anyl- 2,2'-azopropane, 0.4 g. laurylsulfate and 160 of water was sealed in a bottle under an atmosphere ofnitrogen and tumbled in a 65 C. water bath for 18 hrs. The resultingemulsion was broken with sodium sulfate. The polymer was isolated byfiltration and washed thoroughly with water. The dried polymer weighed28.8 g. (72% Elemental analysis indicated that the material was acopolymer of acrylonitnile and 3-dimethylamino-2,2,4,4tetramethylcyclobutanol methacrylate. This polymer was dissolved indimethylformamide and dry spun to give strong fibers. These fibers weremore readily dyeable and exhibited a better afiinity for dyes than didunmodified polyacrylonitrile fibers.

The present invention thus provides a new and useful class ofcyclobutane derivatives.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereina-bove and as defined in the appendedclaims.

I claim:

1. A cyclobutane derivative having the formula:

wherein X is a tertiaryamino group having the formula selected from theclass consisting of:

wherein Y and Z are each alkylene of 2 to 4 carbon 10 atoms; wherein R RR and R when taken singly, are each selected from the group consistingof:

(a) hydrogen, (b) alkyl of 1 to 18 carbon atoms, p y (d) lower alkylsubstituted phenyl, (e) benzyl, (f) allyl, (g) carbalkoxy wherein thealkyl moiety is lower alkyl,

and (h) thienyl; and wherein the substituents R and R and R and R whentaken collectively with the carbon atom to which they are attached,represent a member selected from the group consisting of:

CH -OH;

CH OH;

and

lectively with the nitrogen atom to which they are attached, represent amember selected from the group con sisting of:

CHg-CH:

CHFCHZ 011 011:

(b) N CH,

0H,0H, CH,-GH,

(c) -N O CHPOH} and CH5CH CH5 CH2 l I J: H, CH;

2. A cyclobutane derivative having the formula R R-J7-C=O R1IICH I R R Rwherein R is alkyl having 1 to 8 carbon atoms.

3. 3-dimethy1amino-2,2,4,4-tetramethylcyclobutanone. 4.2,2,4,4-tetramethyl-3-piperidinocyclobutanone.

R6 and forming a cyclobutaue derivative having the formula:

x B o-:0

X,CH +11 wherein X is a tertiaryamino group having the formula selectedfrom the class consisting of:

wherein Y and Z are each alkylene of 2 to 4 carbon atoms; wherein R R Rand R when taken singly, are each selected from the group consisting of(a) hydrogen, a

(b) alkyl of 1 to' 18 carbon atoms,

(d) lower alkyl substituted phenyl,

(e) benzyl,

(g) carbalkoxy wherein the'alkyl moiety is loweralkyl,

and r a (h) thienyl; and wherein the substituents R and R and R and Rwhen taken collectively with the carbon atom to which they are attached,represent a member selected from the group consisting of:

GHQ-CH3 (a) (a) =0 55 GE -CH, and b C/OH2 CH3()H ()3) 1'2, 7 z O=CCRz Y\CHE-CH2 60 N N 0 CH a \ZJ r (c) |L wherein Y and Z are each alkylene of2 to 4 carbon E (1H atoms; wherein R R R and R when taken singl 5 areeach selected from the group consisting of: C'H GHCH hydrogen, 7 (d) E(b) alkyl of 1 to 18 carbon atoms,

| p y (d) lower alkyl substituted phenyl, and 7 (e) benzyl,

(f) a y a V 0 CH2 (g) carbalkoxy wherein the alk l moiety is loweralkyl, I OH I I and o 3* 3 (h) thienyl; a 75 wherein the substituents Rand R and R and R when 12 V wherein R and R ,'when taken singly, areeach selected from the group consisting of: 1 a p (a) alkyl of'1 to 8carbons;

(b) benzyl, and

(c) cyanoethyl, v

and wherein the substituents R and R when talcen collectively with thenitrogen atom'to which they are attached, represent a member selectedfrom the group consisting of: r

CHz-CHg C'H -CH,

CHg-CH3 1 7 a CHr-CHg GH3-CH3 (e) N /O CH;CH

and

05 -011 (d) IL CH;:' OH; We H1 GE -CH the reaction temperature being inthe range of 8 0 C. to 200 CJWhen none of the substituents R R R and Rare hydrogenand in the range of C, to less than the temperature ofthermal decomposition of the tertiaryamino cyclobutanone when at leastone of the substituents R1, R R and R is hydrogen.

13. The process which comprises reacting a compound having the formula 13 l 4 taken collectively with the carbon atom to which they are with acompound having the formula attached, represent a member selected fromthe group R consisting of:

o==0 UHF-CH; 5 R/ at a temperature in the range of 0 C. to 100 C. and

GET Hz forming a cyclobut-ane derivative having the formula /0H,-0H= 1'1(b) :0 /CH; R- [3- |3=0 GHQ-CH2 RN-CH(I1R R n I wherein R is an alkylradical having 1 to 8 carbon atoms. CH 15. The process which comprisesreacting a compound having the formula CH3 CH CH-QH R\ /R1 H N-CH=O 2(d) =O (;H H R R3 and with a compound having the formula K E E c=o=o CH3(8) CH (B CH R6 P 3 at a temperature in the range of 80 C. to 10 C. andH-CHz forming a cyclobutane derivative having the formula wherein R andR when taken singly, are each selected from the group consisting of:R2C-C=O (a) alkyl of 1 to 8 carbons, (b) benzyl, and l (c) cyanoethyland wherein the substituents R and R when taken collectively with thenitrogen atom to which they are attached, represent a member selectedfrom the group consisting of:

wherein R is an alkyl radical having 1 to 8 carbon atoms and wherein R RR and R are selected from the class consisting of hydrogen and alkylradicals having 1 to 8 carbon atoms, at least one of said R R R and Rbeing hydrogen.

CHPCHI 16. The process which comprises reacting dimethyl- (3) 40 ketenewith N,N-dimethylisobutenylamine at a tempera- CHFCHz ture in the rangeof 0 C. to 100 C. andformmg3-dimethylamino2,2,4,4-tetramethylcylobutanone -17. The process whichcomprises reacting dimethyl- 2 ketene wit-h N-isobuteny-lpiperidine at atemperature in the range of 0 C. to 100 C. and forming 2,2,4,4-tetra-CHPCH, methyl-3-piperidinocyclobutanone. 18. The process which comprisesreacting ethylmethyl- (c) ketene with N,N-dimethylisobutenylamine at atemperas- 2 ture in the range of 0 C. to 100 C. and forming3-dimethy1amino-4-ethyl-2,2,4-trimethylcyclobutanone. and -19. Theprocess which comprises reacting dimethyl- CH2 CH ketene withN-isobutenylmorpholine at a temperature in the range of 0 C. to 100 C.and forming 2,2,4,4-tetr-a- CH2 methyl3-morpholinocyclobutanone.

3H: (3H1 20. The process which comprises reacting dimet-hylketene with N(2-ethyl-1 butenyl) piperidine at a temperature in the range of 0 C. to100 C. and forming the reaction temperature being in the range of -80 C.2,2-diethy1-4,4-dimethyl-3 piperidinocyclobutanone.

to 200 C. when none of the substituents R R R and R are hydrogen and inthe range of 80 C. to i less than 10 C. when at least one of thesubstituents R R R and R is hydrogen.

References Cited by the Examiner UNITED STATES PATENTS 14. The processwhich comprises reacting a compound 8/62 Kuna et a1 260*563 X having theformula OTHER REFERENCES R R Opitz et a1. Angew. Chem., Vol. 73 p. 654(1961).

IRVING MARCUS, Primary Examiner. R R

WALTER A. MODANCE, Examiner.

1. A CYCLOBUTANE DERIVATIVE HAVING THE FORMULA:
 12. THE PROCESS WHICHCOMPRISES REACTING A COMPOUND HAVING THE FORMULA: